Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0209—Esters of carboxylic or carbonic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/90—Regeneration or reactivation
  • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J38/00—Regeneration or reactivation of catalysts, in general
  • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
  • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
  • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/882—Molybdenum and cobalt

Definitions

• the present invention relates to a hydrotreatment catalyst, its method of preparation and the use of this catalyst in a process for the hydrotreatment and / or hydrocracking of hydrocarbons, in particular hydrocarbons obtained from boiling range petroleum fractions. between 40 and 560 ° C.
• the Applicant has therefore sought, firstly, to make more efficient known catalysts based on refractory oxide (s) and metals of groups VIB and VIII, and to give them at least equivalent desulfurization and denitrogenation activities. and secondly, to improve the activity of regenerated hydrotreatment catalysts in order to increase the number of recycling cycles and to delay their disposal and destruction.
• This sulphurization can be done either in situ in the refinery's hydrotreatment reactor, or ex situ.
• the sulfurization may be carried out by means of hydrogen sulphide, mercaptans, organic sulphides, polysulfides and / or elemental sulfur, these compounds being introduced alone, mixed with a solvent or at the same time as the feedstock.
• the sulphurization and the preliminary modification can be done in situ, that is to say in the hydrotreatment / hydroconversion reactor, or ex situ, that is to say in a dedicated reactor. It is also possible to envisage a prior ex situ modification combined with an in situ sulphurization in the hydrotreatment / hydroconversion reactor.
• the range of usable organic compounds is quite wide.
• Catalysts modified with C2-14 monoesters are described in patent applications EP 466,568 and EP 1046424. All these compounds are intended to improve the efficiency of the catalysts in hydro-treatment, more particularly in hydrodesulfurization. However, these modifications do not always make it possible to increase sufficiently the performances of the catalyst to meet the specifications concerning the sulfur contents of the fuels which are becoming more and more binding for the refiners. For example, according to the directives of the European Parliament and the European Council, the countries of the European Community must produce diesel fuel containing less than 50 ppm of sulfur from 2005 and less than 10 ppm by 2008 - 201 1 while the 2004 standard is 350 ppm.
• the Applicant has devised a new type of hydrotreatment catalyst, based on refractory oxides and metals of groups VIB and VIII of the periodic table, which, after sulfurization, has a greatly improved activity in desulfurization. as well as denazotation.
• the subject of the present invention is therefore a hydro-treatment catalyst, comprising a support based on at least one refractory oxide, at least one Group VIII metal and at least one Group VIB metal of the Periodic Table of Elements, characterized in that it further comprises at least one organic compound, comprising at least two carboxylic ester functions, of formula (I) or (II)
• each R 1 is independently C 1 -C 18 alkyl, C 2-18 alkenyl, C 8 -C 18 aryl, C 3 -C 8 cycloalkyl, C 7-20 arylalkyl or arylalkyl, or both R 1 groups form, together, a divalent C2-18 group
• R2 represents a C1-C18 alkylene, C6-C18 arylene, C3-7 cycloalkylene group, or a combination thereof, the carbon chain of the hydrocarbon groups represented by R1 and R2 being contain or carry one or more heteroatoms selected from
• the Applicant has established that the presence on the catalysts of at least one organic compound of formula (I) or (II) increases the desulphurization and denitrogenation efficiency of the catalysts, after activation by sulfurization under known conditions.
• these novel catalysts for the hydrotreatment of hydrocarbons, in comparison with equivalent catalysts which have not undergone any prior modification, it is possible to lower the desulfurization reaction temperature by about 5 to 20 ° C. residual sulfur given and all operating conditions being identical elsewhere (pressure, amount of hydrogen and hourly space velocity (WH)).
• WH hourly space velocity
• Such a gain in activity makes it possible to envisage obtaining residual sulfur contents which are clearly lower than 50 ppm, or even less than 10 ppm, in the hydrocarbons treated, by varying the operating conditions. If the unit is already able to produce a low-sulfur oil cut, this gain in activity will reduce the reactor temperature to produce the desired sulfur content, and thereby maintain the unity of the unit. service for an additional period of up to several months.
• Formulas (I) and (II) of the organic compound used in the present invention include compounds having two, three or four ester functions, or more.
• the residues R 1 and R 2 generally do not comprise other ester substituents and the organic compound of formula (I) or (II) is a diester.
• C O of formulas (I) and (II) is preferably equal to 1, 2 or 4, and in particular equal to 1 or 2.
• alkyl ortho-phthalates alkyl isophthalates, alkyl terephthalates, esters of malonic acid, of adipic acid, of glutaric acid, 1,6-dioxacyclodecane-2,5-dione, dimethyl 2- (methoxymethyl) succinate, dibutyl itaconate, diethyl 2,3-diacetylsuccinate, cyclohexane-1,4-dicarboxylate of dimethyl, 3,3'-dithiodipropionate dimethyl.
• the compound of formula (I) is a C 1 -C 4 dialkyl succinate, preferably dimethyl succinate.
• the unmodified catalyst known per se, is a catalyst consisting of a refractory oxide support of the alumina, silica or silica-alumina type containing from 0.1 to 10% by weight of at least one metal of the group VIII, preferably nickel and / or cobalt, and from 1 to 20% by weight of at least one Group VIB metal, preferably molybdenum.
• the catalyst may be a fresh, i.e., unregenerated, catalyst directly from a manufacturer, but the pretreatment according to the invention by one or more compounds of formula (I) or (II) is also useful when it is a regenerated catalyst, generally by a suitable chemical or thermal treatment, for example by calcination. It is nevertheless known that some fresh catalysts, because of a specific method of preparation, may be more or less refractory to the recommended treatments. In the same way, for the same reasons or following particular operating conditions experienced in the unit, the regenerated catalysts may be more or less refractory to these treatments.
• the catalyst according to the invention preferably contains at least
• the invention also relates to a process for preparing the modified hydrotreatment catalyst described above.
• This modification process comprises contacting a catalyst comprising a support based on at least one refractory oxide, at least one Group VIII metal in the oxide state, and at least one Group VIB metal to the oxide state, with at least one organic compound of formula (I) or (II)
• the contacting is generally and preferably an impregnation.
• the contacting can be carried out in the absence of solvent.
• the unmodified catalyst is brought into contact with the organic compound (s) of formula (I) or (II) preferably by contacting the catalyst with a solution containing the agent (s) ) organic (s).
• the volume of solution may be less than, equal to or greater than the pore volume of the catalyst.
• the method using a volume of solution less than the pore volume of the catalyst is sometimes called "dry impregnation".
• the excess solution will be removed after the adsorption of the organic compound (s) of formula (I) or (II) on the catalyst.
• (I) or (II) may be in the presence of at least one solvent.
• the organic compound (s) of formula (I) or (II) is (are) preferably at least partially soluble in the solvent used.
• the choice of the solvent is of particular importance in the implementation of the process.
• the selection of the solvent is based on various criteria such as its solvent power of the compound (s) of formula (I) or (II), its dispersing effect of the compound (s) of formula (I) or (II), its wetting effect of catalyst surface and its availability on the market under economically acceptable conditions.
• solvents advantageously used in the invention include water, supercritical fluids such as carbon dioxide, aromatic solvents, aliphatic, alicyclic, petroleum cuts, mono- and polyhydroxy solvents such as ethanol, tert-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol (PEG), glycerol, alkyl esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, N-methylpyrrolidone, amide-containing solvents such as dimethylacetamide, nitrile-containing solvents such as acetonitrile, alkyl carbonates such as ethyl carbonate, ethers such as tetrahydrofuran, sulfur-containing solvents such as dimethylsulfoxide and sulfolane, acids such as acetic acid, and halogenated solvents, or a mixture of several of these solvents.
• supercritical fluids such as carbon
• water, toluene, xylenes, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethanol, tert-butanol, polyethylene glycol (PEG), most often of molecular weight, are particularly preferred. from 1 18 (triethylene glycol) up to 1000, white spirit and petroleum ether.
• the organic compound (s) of formula (I) or (II) may optionally be introduced in the presence of at least one acid, generally chosen from carboxylic acids, Hydrocarboxylic acids and polyacids (such as formic, acetic, glycolic, lactic, tartaric, maleic, citric, glyceric, gluconic, methoxyacetic, ethoxyacetic, malonic, L (+) ascorbic, salicylic, oxalic, orthophthalic, succinic, glyoxylic Among, thiocarboxylic acids (such as thiobenzoic acid, mercapto acetic acid, 1 and 2 mercapto-propionic, 2-3 dimercapto succinic, mercapto succinic, thioacetic, thioglycolic, thiodiglycolic, dithiodiglycolic Among, aminocarboxylic acids (nitrilotriacetic acid, EDTA (ethylenediamine diammonium
• the particularly preferred acids are lactic acid, maleic acid, tartaric acid, citric acid, succinic acid, oxalic acid and thioacetic acid. e, thioglycolic, nitriloacetic, and EDTA.
• the acid (s) may be introduced with the compound (s) of formula (I) or (II), or separately, if, for example, the mixture obtained is not homogeneous.
• the catalyst is brought into contact, optionally pre-dried between 10 and 600 ° C., preferably between 15 and 300 ° C., and more preferably between 20 and 180 ° C., with a solution of one or more compounds of formula ( I) or (II) during the impregnation stage can last from 1 minute to 7 days, preferably from 10 minutes to 8 hours, at a temperature of between 0 ° C. and 200 ° C., preferably at ambient temperature, at a low pressure of between atmospheric pressure and 5 bars, preferably at atmospheric pressure.
• the catalyst can be subjected, optionally after removal of an excess of impregnation solution, to an optional maturation stage at a temperature generally of from 0 to 100.degree. the ambient temperature (approximately 20 ° C.) at 80 ° C., generally at atmospheric pressure or up to the pressures generally used in hydrotreatment or hydroconversion processes, the duration of which may be between a few minutes and a few years in the case where the catalyst remains stored in drums.
• the ripening step can last from a few minutes to 2 days.
• An optional heat treatment subsequent to the maturation step may be carried out at temperatures of from 50 ° C.
• the optional steps of maturation and heat treatment may optionally be omitted when the catalyst is loaded directly into the hydrotreating or hydroconversion unit.
• the catalyst modified by impregnation with the compound (s) of formula (I) or (II) is perfectly stable at room temperature and in air.
• the modification of the catalyst can therefore be carried out ex situ, that is to say outside a hydrotreatment reactor, generally hydroconversion, and this is a preferred embodiment of the process according to the invention.
• Ex situ implementation of the method according to the invention may optionally be combined with ex situ sulphurisation of the modified catalyst according to the invention. This allows the refiner to purchase a product immediately ready for use and to minimize the time lost when starting the unit.
• the preparation process according to the invention is characterized in that the contacting of the catalyst with the compound (s) of formula (I) or (II) is in the presence of hydrogen and at least one sulphurizing agent preferably chosen from hydrogen sulphide, elemental sulfur, CS2, mercaptans, sulphides and / or polysulphides, hydrocarbon cuts with a boiling point below 400 ° C. containing compounds sulfurous, generally within a hydrotreating reactor.
• the organic compound (s) of formula (I) or (II) may be incorporated into the support even before the compounds of groups VIB and VIII are deposited. This can be done by mixing one or more organic compounds with the components of the support before shaping it, or by impregnating the support formed with the organic compounds.
• Another possibility is to introduce the organic compound (s) and the compounds of the metals of groups VIB and VIII simultaneously, either by mixing them with the components of the support before shaping, or by impregnating a support already shaped with the the organic compound (s) and the salts of Group VIB and VIII metals.
• One or the other of the operations may be followed by drying, carried out under conditions such that at least part of the organic compounds is retained in the catalyst.
• organic compound (s) of formula (I) or (II) may be introduced into the catalyst in liquid form and / or particulate solid and / or in the form of a solution or suspension in a suitable solvent.
• the invention further relates to a process for the in situ or ex situ activation of a hydrotreatment catalyst as described above.
• This activation is carried out by bringing the catalyst into contact simultaneously or successively with hydrogen and at least one sulfurization agent preferably chosen from hydrogen sulphide, elemental sulfur, CS2, mercaptans, sulphides and / or or polysulfides, hydrocarbon cuts with a boiling point below
• a preferred sulfurizing agent is dimethyl disulfide (DMDS).
• the sulphurizing agent may be introduced in the form of a gas or in diluted form in a solvent, or as an additive of the feed to be hydrotreated.
• the invention finally relates to the use of the catalyst thus activated in situ or ex situ, for the hydrotreatment and / or hydrocracking of hydrocarbons, in particular hydrocarbons from petroleum fractions with a boiling point between 40 and 560 ° C.
• hydrocarbons in particular hydrocarbons from petroleum fractions with a boiling point between 40 and 560 ° C.
• the examples given in the remainder of the present description are intended to illustrate and not to limit the invention.
• Example III a method of preparation of the catalysts according to the invention is described, these catalysts being then used in Example III.
• Catalyst A consisting of a combination of 3% by weight of cobalt and 10% by weight of commercially available alumina-supported molybdenum commonly used by refiners in commercial units. hydrodesulfurization.
• This catalyst A with a compound of formula (I) is as follows: 200 g of catalyst A are placed in the flask of a rotary evaporator rotated at 45 rpm. A solution consisting of 53.3 g of dimethyl succinate dissolved in 66 ml of toluene is injected over 35 minutes into the core of the catalyst. The impregnated solid is left for 16 hours in slow rotation (20 revolutions per minute) before being subjected to a reduced pressure, equal to 2700 Pa, and a temperature of 50 ° C. for 30 minutes. After evaporation of most of the toluene, a catalyst with a dry appearance is obtained.
• catalyst B After 1 day at room temperature, 100 ml of this catalyst was charged to a pilot diesel oil desulphurization unit reactor for carrying out an activity test as described in Example III. After loading, the catalyst undergoes a heat treatment at 180 ° C. for 2 hours, then another heat treatment at 150 ° C. for 14 hours, all under a nitrogen flow of 20 l / h. The catalyst thus obtained is called catalyst B.
• Example III there is described a mode of preparation of the catalyst according to the invention in the absence of solvent. This catalyst is then used in Example III.
• Catalyst A 100 g of Catalyst A are placed in the flask of a rotary evaporator and then rotated at 45 rpm. 54.8 g of dimethyl succinate are injected over 12 minutes into the catalyst core. The impregnated solid is then heated at 50 ° C for 30 minutes to accelerate dispersion of the liquid in the catalyst. After 49 days of storage at room temperature, 100 ml of this catalyst are charged into the reactor of the diesel fuel desulphurization pilot unit in order to carry out the activity test described in Example III. The catalyst is heat-treated at 150 ° C. for 16 hours under a nitrogen flow of 20 l / h. This catalyst according to the invention is called catalyst C.
• Each of the catalysts B and C (according to the invention) is sulphurized with a gas oil supplemented with 2% by weight of dimethyl disulphide (DMDS) according to the procedure recommended by the catalyst manufacturer A.
• DMDS dimethyl disulphide
• the activity of the catalysts B and C modified according to the invention is compared with that of the catalyst A having undergone no modification treatment.
• a charge is introduced comprising a mixture of 70% by weight of gas oil and 30% by weight of a hydrocarbon fraction LCO type (Light Cycle OzZ) from catalytic cracking.
• LCO type Light Cycle OzZ
• the hydrotreatment reaction is carried out under a pressure of 27.10 5 Pa (27 bar) with a hydrogen / hydrocarbon ratio (H 2 / HC) of 250 Nl / l at a hourly space velocity (WH) of 1 h -1 .
• the reaction temperature is adjusted for each catalyst to a value corresponding to a desulfurization rate of 99%.
• the catalysts B and C according to the invention make it possible to reach a desulfurization rate of 99% at a temperature that is lower than 70 ° C. than that required for the catalyst A. They therefore have a much higher hydrosulfurization activity than that of catalyst A.
• the residual nitrogen content for each reaction catalyst is measured for a given reaction temperature (THDN). The lower this residual nitrogen content, the more the catalyst is active in denitrogenation.
• the catalysts B and C according to the invention make it possible to lower the residual nitrogen content more strongly than the catalyst A, which shows that they are also more active in denitrogenation.

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• 2005
  • 2005-01-20 FR FR0500579A patent/FR2880823B1/fr active Active
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